Photography



' Patented Feb. 7, 1928.

UNITED STATES NATHAN SULZBERGER, OF NEW YORK, N. Y.

PHOTOGRAPHY.

NdDrawing. Application filed June 4,

This invention relates to improvements in photography. More particularly, it relates to an improved process of developing pictures or images on films, plates, paper, etc.,

5 and to the developed pictures or images on such material as new products.

I have discovered that warm sepla-like tones can be produced not only on paper, but also on plates and films by direct development, particularly with a hydroxyl-amrndeveloper, as hereinafter more fully described; and the resulting developed pictures or images areditferent from pictures or images with sepia-like tones heretofore produced.

Sepia tones have heretofore been produced on paper by redevelopment. In the redevelopment of pictures (on paper) for the production of sepia tones, the developed black and white picture is first bleached 1n an oxidizing bath, and is then redeveloped by treatment with a sulfide bath which pro,- duces a sulfur compound with the silver of the paper, so that the redeveloped picture -1s different from the original silver image of the black and white picture before redevelopment.

In motion picture films attempts have been made to produce sepia-like tones by tinting, but this requires additional operations, time and work, and has the further disadvantages that the dye used also covers all the whites and that the tinted films are easily stained by the oil in the projection machines,whicli disturbs the proper projecting of the picture. The tinted films may also be affected by light-rays and wear and may be non-uniform, where the tinting is not uniformly and carefully applied.

According to the present invention, warm sepia-like tones are produced by direct development, and can be produced not only on paper, but also on plates and particularly on positive motion picture films, which can then be projected and will give a warmer tone of the projected picture, as distinguished from the cold or colorless black and white pictures commonly projected.

In referring to the tones produced according to the present invention as warm sepialike tones, I do not limit myself to brownish tones, but include olive tones, reddish tones, and other tones, other than black, which are and can be produced by my direct development. The tones depending on exposure, formulae, conditions and materials used which I consider particularly valuable are 1923. Serial No. 643,420.

warm brownish tones similar to the sepia, or Van Dyke brown or etching brown tones which have been heretofore produced by redevelopment on paper. These tones. are moreover silver tones (reduction products of the original silver compounds) produced by the direct development as distinguished from the sulfide pictures, etc. produced by redevelopment. It is also possible to produce by the process of the present invention, in cases, when that is desired, black tones as well. Under given conditions and material, uniform results can be obtained, while, heretofore, such other than black tones were generally obtained on papers under more or less forced conditions (redevelopment, hypoalum, restrainers, higher temperature, sodium hydrate, etc.) and were often peculiar- 'ly affected and ,uncontrollably modified in the fixing bath.

In carrying out the process of the present invention, I prefer to make use of a phenylhydroxyl arnin developer, or an aromatic hydroxyl-amin developer, and I use the term hydroxyl-amin to include not only a phenyl-hydroxyl-amin developer, but also homologues, salts, derivatives, substitution products, etc. as well as mixtures or compounds containing the same. A particularly valuable developer is made by combining phenyl-hydroxyl-amin with an organic acid such as oxalic acid, as more fully described in my prior application Serial No. 491,296, filed August 10th, 1921. As pointed out in said application, compounds which are relatively stable in character can be produced by combining phenyl-hydroxyl-amin with organic acid, and particularly with oxalic acid; and I find such developers particularly advantageous for use in the process of the present invention. I do not limit myself,

however, to the use of such organic salts, but

consider the invention of broader scope and application, and, in the broader and more comprehensive claims appended hereto I intend to include other hydroxyl-amin compounds than the salts of phenyl-hydroxylamin with organic acid, such as other phenyl-hydroxyl-amin compounds or derivat1ves, homologues, organic and inorganic salts, substitution products, also-of the acids employed, mixtures etc., Wl'llCh have the property of acting in a similar or modified way to give the desired tones by. dlrect development. Compounds also other than hydroxylamin salts (organic and inorganic) etc. which will give sepia, etc. like tones particularly on moving picture posi tive films by direct (tank etc) development, shall also be considered as coming under the scope of this invention.

'In usingthe hydroxyl-amin developer, I have found that it can advantageously be used with sodium sulfite which exerts a protective influence. The following formula,

for example, can'be advantageously employed for producing a sepia-like tone on glass plates or on films (transparent material):

Water 900 cc.

Sodium sulfite 20 grams. Phenyl-hydroxyl-aminoxalate 4 grams. Hydroqninone 2 grams. Sodium carbonate 22 grams. Potassium bromide 4-8 drops of a 10% potassium bromide solution per each 30 cc. of the above solution.

Sodium sulfite 15 grams. Phenyl-hydroxyl-aminoxalate 1 gram. Hydroquinone 4 grams. Sodium carbonate 22 grams. Potassium bromide 4-8 drops of a 10% potassium bro mide solution per each 30 cc. of the above solution.

-- The ingredients are dissolved in the order given.

It will be noted that in the above formulae there is no. free caustic alkali used, the formulae containing only sodium carbonate as the alkaline material.

These specific formulae can be varied. In

the above fo'rmalae, it will be noted that the phenyl-hydroxyl-amin oxalate is compounded 4 with sodium sulfite and sodium carbonate as well as with other developer ingredients, such as hydroquinone and potassium bromide. The sodium sulfite contributes to the developer composition and also has a protective influence upon the solution. In fact, samples of developerhave been kept experimentally for many months and worked satisfactorily, the liquid remaining water-clear and not discoloring. Other substances (potassium metabisulphite etc. etc.) having a similar or .modified action can be employed. Variations and modifications can be made both in the (aromatic) hydroxyl-amin compound and in the ingredients with which it is employed without departing from the invention. For example, other phenyl-hyroxylamin compounds, salts, homologues, derivatives, substitution products, etc., may be used, as well as other photographic developer ingredients, as, for example, restrainers, hke borax, sodium oxalate and citrate (particularly for bromide papers, etc), etc. No caustic alkali being used in these formulae, it is particularly pointed out that the developer does not annoy or affect the fingers and hands, nor make the material handled slippery.

In using the developer or developing composition in the carrying out of the process of the present invention, the developer can be diluted with water to the desired extent, e. g. to the extent indicated in the above formulae, and then used for developing the paper or the plate or film in much the same manner, with subsequent fixing, that other developing solutions are used, but with the important distinction and advantage that a warm tone, as well as a black tone, if desired, can be directly produced as a result of the development. In the case of films, such as positive motion picture films, the film can be run through the developing bath (tank) in the ordinary way, and then through the fixing bath to give by direct development a warm brownish or sepia-like tone which projects with awarm tone more agreeable than the ordinary black and white developed film, wighout it being necessary to pass through a ye.

The image or picture thus developed may be either on paper, or on glass or film. Negatives can be similarly developed, but I con sider the invention of special value for the direct development of positive pictures and images, and especially for positive motion picture films because of the advantages resulting from the application of the invention to such film, giving as it does, directly a warm silver picture in which the warm tone is in the silver and its direct reduction products. When in the claims I refer to a silver picture and to reduction products of silver I mean the picture obtained by direct development and which is or may be fixed in the usual way in a hypo bath, as distinguished from pictures which have been llU specially treated by tinting or by redevelopinent, with hypo-alum etc. to give a sepialike tone.

The resulting directly developed sepia-like toned picture or film as, for example, obtained by my phenyl-hydroxl-amin oxalate developer is very valuable and I consider it to be anentirely new photographic product. These Warm (i. e. other than black) tones are more agreeable than the harsher black and white tones commonly produced by direct development. They may, as above pointed out, be of various shades, such as olive, reddish, brownish, sepia-like, etc., depending on exposure, conditions and material (nature and quantity) iised. These warm tones, moreover, may be produced not only on paper where they give a warm sepiatone picture, but also on plates, lantern-slides and, particularly, on films (transparent material), such as positive motion picture films where the warm tones of the developed image can be projected and will give on the the hydroxl-amin developer is advantageously used in combination with hydroquinone, e. g. as described in the above examples, or

' in my prior application, Serial No. 491,296.

I have'found, however, that it can also be used to advantage in place of hydroquinone \Vater 900 cc. Sodium sulfite 20 grams. Phenyl-hydroxyl-aminox ate 2grams. Metol (mono-alkyl derivatlve of an amidophenol)- 4 grams. Sodium carbnatc 22 grams. Potassium bromide 4-8 drops of a potassium bromide solution per each 30 cc. of the above solution.

The ingredients of these respective formulm are dissolved in the water in the order mentioned. In both formulae hydroqumone is omitted and the phenyl-hydroxyl-amin 6th, 1921, and in my said prior application,

Serial No.-491,296. The same, as well as other compounds coming under this invention, may be put up in compressed (tablet) form alone or in mixture with suitable other developers or developeringredients (metol, pyrogallic acid, etc.).

Tests with an hydroxyl-amin substance (phenyl-hydroxyl amimoxalate) as a furdyedyed 12 hours with addition of hydro-v gen peroxideproved its fastness to light, standing up better than paraphenylen-diamin.

I claim:

1. The method of producing a Warm tone by direct development, which comprises subjecting photographic material containing photo-sensitive silver compounds to the action of a developer comprising hydroxylamin oxalate.

2. The method of producing a warm tone by direct development, which comprises subjecting photographic material containing photo-sensitive silver compounds to the action of a developer comprising an aroin metol (mono-alkyl derivative of an amidophenol), pyro, and other developer formulae, and that when so used, particularly fine black and white pictures or images can be directly produced which are distinguished from the Warm tones hereinbefore referred to. In many cases, a soft film, etc. negative (black and white) and less contrasty may be thus obtained.

The following formulae can be advantageously employed for producing beautiful soft black tones on paper:

Water 900 cc. Sodium sulfite 20 grams. Phenyl-hydroxyl minoxalate 3 grams. Pyrogallic acid l. 2 grams. Sodium carbonate 22 grams. Potassium bromide 4-8 drops of a 10% potassium bromide solution per each 30 cc. oftlie above solution.

matic hydroxyl amin salt of an organic acid.

3. The method of producing a warm tone by direct development, which comprises subjecting photographic material containing photo-sensitive silver compounds to the action of a developer comprising an aromatic hydroxyl-amin substance and a sulfite.

4. The method of producing a warm tone by direct development, which comprises subjecting photographic material containing photo-sensitive silver compounds to the action of a developer comprising an aromatic hydroxyl-amin substance and hydroquinone.

5. The method of producing a warm tone by direct development, which comprises sub jecting photographic material containing photo-sensitive silver compounds to the action of a developer comprising an aromatic hydroxyl-amin substance, hydroquinone, sodium sulfite and sodium carbonate.

6. The method of producing a warm tone by direct development, which comprises subjecting photographic material containing photo-sensitive silver compounds to the action of a developer comprising an aromatic hydroxyl-amin substance, hydroquinone, sodium sulfite, sodium carbonate and potassium bromide.

7. The method of producing a warm tone by direct development, which comprises subjecting photographic material containing photo-sensitive silver compounds to the action of a developer comprising phenyl-hydroxyl-amin oxalate.

8. The method of directly developing apositive moving picture film to a sepia or brownish tone which comprises subjecting the film in a continuous manner to the action of a developer containing in solution a compound of phenyl-hydroxyl-amin with an organic acid.

.9. The method of producing directly on surface coated with photo-sensitive material a sepia like tone which comprises subjecting the same to the action of a developer containing dissolved phenyl-hydro yl-amin oxalate and hydroqulnone.

10. Photographic material having a picture tor image of warm tone produced by direct development, the image consisting of the reduction product obtained by the action of an hydroXyl-amin substance on the photosensitive silver compound.

11. A soft sepia-like picture or image, being a silver image produced by the reduction and direct development of photosensitive silver material with an hydroxylamin-oxalate.

12. Photographic material having a picture or image of warm tone produced by direct development of photo-sensitive silver compounds by an hydroxyl-amin developer.

13. A colored silver image produced by direct development of photo-sensitive silver material with a developer containing an organic salt 01": an aromatic hydroXyl-amin.

14. A positive motion picture film having an image of warm sepia-like tone produced by the reduction of the silver of the film by a solution comprising phenyl-hydroxylamin oxalate.

15. A positive motion picture film having a reduced silver image of warm sepia-like tone produced by the direct development of the photo-sensitive silver compound with a hydroxyl-amin substance and hydroquinone.

16. A sepia toned silver picture on motion picture film produced by the development. of a photo-sensitive silver compound with a hydroxyl-amin substance, such sepia image being practically insoluble in projection-machine oil.

17. A positive moving picture strip of film bearing images of warm tone not permanently detrimentally staining, when coming in contact with the oil of the projection machine, the colored images consisting of silver compounds treated with hydroxylamin developer.

In testimony whereof I aflix my signature.

NATHAN SULZBERGER. 

